EP2225323B1 - Rubber mixture, particularly for vehicle tires - Google Patents

Rubber mixture, particularly for vehicle tires Download PDF

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Publication number
EP2225323B1
EP2225323B1 EP08861687.5A EP08861687A EP2225323B1 EP 2225323 B1 EP2225323 B1 EP 2225323B1 EP 08861687 A EP08861687 A EP 08861687A EP 2225323 B1 EP2225323 B1 EP 2225323B1
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EP
European Patent Office
Prior art keywords
rubber
phr
styrene
rubber mixture
mixture according
Prior art date
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Application number
EP08861687.5A
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German (de)
French (fr)
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EP2225323A1 (en
Inventor
Christian Weber
Carla Recker
Katharina Herzog
Marc Laschet
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Continental Reifen Deutschland GmbH
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Continental Reifen Deutschland GmbH
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
    • B29B7/7495—Systems, i.e. flow charts or diagrams; Plants for mixing rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L19/00—Compositions of rubbers not provided for in groups C08L7/00 - C08L17/00
    • C08L19/006—Rubber characterised by functional groups, e.g. telechelic diene polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers

Definitions

  • the invention relates to a rubber mixture, in particular for vehicle tires.
  • the driving characteristics of a tire depend to a large extent on the rubber composition of the tread, particularly high demands are placed on the composition of the tread compound.
  • the desired properties are abrasion, rolling resistance, as measured by the rebound resilience, and wet grip.
  • an improvement in one tire property often results in a deterioration of another property.
  • abrasion resistance in a given mixing system, there are several known ways to increase the abrasion resistance. Worth mentioning here are the reduction of the glass transition temperature of the rubber mixture, the optimization of the degree of filling and the change of the polymer system. All these measures inevitably lead to a deterioration of the wet grip properties of the given mixture.
  • phr parts per hundred parts of rubber by weight
  • the dosage of the parts by weight of the individual substances is always based on 100 parts by weight of the total mass of all the rubbers present in the mixture.
  • D1 discloses a diene rubber compound having as a main component a solution-polymerized styrene-butadiene copolymer having a glass transition temperature of not lower than -50 ° C. Not less than 40% by weight to less than 65% by weight of the polymer chains of the solution-polymerized styrene-butadiene copolymer are modified with silicon tetrachloride and the styrene-butadiene copolymers have 40% by weight or less of vinyl bonds in the butadiene.
  • the rubber composition here contains a conjugated diene polymer A and a conjugated diene polymer B whose glass transition temperature is 20-80 ° C lower than that of the polymer A and an inorganic filler.
  • Polymer B is a modified butadiene polymer or a stryol-butadiene copolymer with 10 to 40 weight percent vinyl content.
  • a rubber blend with two different copolymers is disclosed in D3 .
  • the first copolymer is modified or functionalized, has a glass transition temperature between 0 and -80 ° C and a vinyl content between 5 and 50 wt.%, While the second copolymer is unmodified and a glass transition temperature between 0 and -80 ° C and a vinyl content between 5 and 50 wt -.% Has.
  • the rubber mixture contains two reinforcing fillers, among other things between 50 and 100 phr of a silica-based filler.
  • D4 discloses a pneumatic tire having a sulfur vulcanizable composition characterized by having from 50 to 90 phr of a rubber having a glass transition temperature in the range of -80 ° C to -110 ° C and 10 to 50 phr of at least one rubber having a glass transition temperature of Ranges from -79 ° C to + 20 ° C and 15 to 50 phr of a non-rubber resin.
  • This blend shows improved lab performance, which correlates with improved tire wear while improving grip and handling.
  • D5 describes an elastomeric, sulfur vulcanizable composition for the manufacture of tires for reducing hysteresis and thus reducing fuel consumption.
  • This blend comprises a blend of from 20 to 100 weight percent of a functionalized elastomer having 10 to 150 phr of silica and having 0 phr of carbon black and 0 to 80 weight percent of a non-functionalized elastomer.
  • D6 describes rubber compositions for tires containing a styrene-butadiene rubber modified with N-methyl- ⁇ -caprolactam and a high molecular weight styrene-butadiene rubber.
  • D7 describes a rubber composition for treads of tires containing an end-group modified styrene butadiene rubber, at least one other rubber and a relatively large amount of silica.
  • the present invention is based on the object to provide rubber mixtures whose vulcanizates are characterized by an increased wet grip, at the same time the rolling resistance remains at the same level or even improved.
  • the rubber mixture contains 20-90 phr, preferably 25-80 phr, more preferably 45-80 phr of at least one natural or synthetic polyisoprene.
  • the butadiene rubber is a high-cis butadiene rubber with a cis content greater than or equal to 90% by weight.
  • At least one end-group-modified styrene-butadiene rubber is present in proportions of from 5 to 50 phr, preferably in proportions of from 10 to 40 phr, in the rubber mixture. It is preferably a solution-polymerized styrene-butadiene rubber or an emulsion-polymerized styrene-butadiene rubber.
  • the styrene-butadiene rubber has a glass transition temperature between -40 ° C and 0 ° C, preferably between -35 ° C and 0 ° C, and more preferably between -30 ° C and -10 ° C.
  • the styrene content of the styrene-butadiene rubber is preferably less than or equal to 50% by weight and / or the vinyl content of the styrene-butadiene rubber is preferably greater than or equal to 10% by weight.
  • the styrene-butadiene rubber is end-group-modified with amino groups and / or alkoxysilyl groups and / or OH groups and / or epoxide groups and / or carboxyl groups and / or mercapto groups.
  • the rubber mixture contains 0-50 phr, preferably at least 0.1 phr, in particular at least 0.5 phr, of at least one further polar and / or nonpolar rubber.
  • the further polar and / or non-polar rubber is in this case selected from the group consisting of liquid rubbers and / or halobutyl rubber and / or polynorbornene and / or isoprene-isobutylene copolymer and / or ethylene-propylene-diene rubber and / or nitrile rubber and / or Chloroprene rubber and / or acrylate rubber and / or fluororubber and / or silicone rubber and / or polysulfide rubber and / or epichlorohydrin rubber and / or styrene-isoprene-butadiene terpolymer.
  • the rubber mixture may also contain other diene rubbers which do not correspond to the characterizing features of claims 1 to 13.
  • the rubber mixture according to the invention also contains 0-7 phr, preferably at least 0.1 phr, in particular at least 0.5 phr, of at least one plasticizer oil, wherein the plasticizer oil is preferably a mineral oil which is selected from the group consisting of DAE (Distilled Aromatic Extracts) and / or RAE (Residual Aromatic Extract) and / or TDAE (Treated Distilled Aromatic Extracts) and / or MES (Mild Extracted Solvents) and / or naphthenic oils.
  • DAE Disistilled Aromatic Extracts
  • RAE Residual Aromatic Extract
  • TDAE Transstilled Aromatic Extracts
  • MES Mild Extracted Solvents
  • This further plasticizer may be a synthetic plasticizer and / or a fatty acid and / or a fatty acid derivative and / or a resin and / or a factor.
  • the rubber mixture contains 0.1-20 phr, preferably at least 0.5 phr, of amorphous silica and / or precipitated silica. All the silicas known to the person skilled in the tire industry can be used.
  • the amorphous silica and / or precipitated silica is attached to the polymer matrix by a coupling agent, preferably at least one silane.
  • the silane is used in proportions of 0-10 phr, preferably in proportions of 0-8 phr, more preferably at least 0.1 phr, especially at least 0.5 phr.
  • the silane coupling agents serve at the same time to improve the processability and to attach the silica and other optional polar fillers to the diene rubber and react with the silanol superficial groups of the silica or other polar groups during the mixing of the rubber or rubber compound (in situ). or even before the addition of the filler to the rubber in the sense of a pretreatment (pre-modification). All silane coupling agents known to the person skilled in the art for use in rubber mixtures can be used as silane coupling agents.
  • the rubber mixture contains 30 - 70 phr of at least one carbon black, preferably having a DPB number 105-150 cm 3 / 100g.
  • the DBP number according to ASTM D 2414 determines the specific absorption volume of a carbon black or a light filler by means of dibutyl phthalate.
  • the rubber mixture may also contain further fillers such as aluminum hydroxide, layered silicates, chalk, starch, magnesium oxide, titanium dioxide, rubber gels, short fibers, etc. in any desired combinations.
  • the rubber mixture contains other additives.
  • Other additives essentially include the crosslinking system (crosslinker, accelerator and retarder), antiozonants, anti-aging agents, masticating agents and activators.
  • the proportion of the total amount of further additives is from 2 to 100 phr, preferably from 3 to 80 phr and more preferably from 5 to 60 phr.
  • the vulcanization of the rubber mixture is carried out in the presence of sulfur or sulfur donors, with some sulfur donors can also act as a vulcanization accelerator.
  • Sulfur or sulfur donors are added to the rubber mixture in the last mixing step in amounts customary to the person skilled in the art (0.4 to 4 phr, sulfur, preferably in amounts of 1.0 to 2.5 phr).
  • the rubber mixture may contain vulcanization-influencing substances such as vulcanization accelerators, vulcanization retarders and vulcanization activators in the usual amounts, which are contained according to the invention in the above-described additives.
  • the preparation of the rubber mixture according to the invention is carried out according to the usual method in the rubber industry, in which first in one or more mixing stages, a base mixture with all components except the vulcanization system (sulfur and vulcanisationsbeeinlende substances) is prepared. By adding the vulcanization system in a final mixing stage, the finished mixture is produced. The finished mixture is further processed eg by an extrusion process and brought into the appropriate form.
  • the vulcanization system sulfur and vulcanisationsbeeinlende substances
  • the rubber mixture is used for the production of pneumatic vehicle tires, in particular a tread and / or a body mixture.
  • body mixtures are here called the mixtures that make up the inner components of a vehicle tire.
  • the mixture is preferably made in the form of a tread and applied as known in the manufacture of the vehicle tire blank.
  • the tread may also be wound up in the form of a narrow rubber mix strip on a green tire.
  • the preparation of the rubber mixture according to the invention for use as a body mixture in vehicle tires is carried out as already described for the tread. The difference lies in the shape after the extrusion process.
  • the thus obtained forms of the rubber mixture according to the invention for one or more different body mixtures then serve the construction of a green tire.
  • the rubber compound is used for the production of belts and straps, in particular conveyor belts, flat belts, V-belts, V-ribbed belts and toothed belts.
  • the extruded mixture is formed into the appropriate shape and often or subsequently reinforced with reinforcing materials, e.g. synthetic fibers or steel cords. In most cases, this results in a multi-layered structure, consisting of one and / or several layers of rubber mixture, one and / or more layers of identical and / or different reinforcement and one and / or several other layers of the like and / or another rubber mixture.
  • the wet grip of the rubber composition is expressed on a laboratory scale by the rebound resilience at room temperature and the rolling resistance by the rebound resilience at 70 ° C.
  • Mixture V1 contains only polyisoprene as the polymer component.
  • the replacement of polyisoprene by butadiene rubber, as represented by V2 worsens the wet grip, making the value of the rebound resilience at RT relatively high without deteriorating the rolling resistance.
  • Replacing it with a non-endgroup modified styrene butadiene rubber having a low glass transition temperature see V4, brings with it the desired wet grip improvement, but at the same time unacceptable degradation of the rolling resistance, thereby lowering the value of the rebound resilience.

Description

Die Erfindung betrifft eine Kautschukmischung, insbesondere für Fahrzeugreifen.The invention relates to a rubber mixture, in particular for vehicle tires.

Da die Fahreigenschaften eines Reifens, insbesondere Fahrzeugreifens, in einem großen Umfang von der Kautschukzusammensetzung des Laufstreifens abhängig sind, werden besonders hohe Anforderungen an die Zusammensetzung der Laufstreifenmischung gestellt. So wurden vielfältige Versuche unternommen, die Eigenschaften des Reifens durch die Variation der Polymerkomponenten, der Füllstoffe und der sonstigen Zuschlagstoffe in der Laufstreifenmischung positiv zu beeinflussen. Prinzipiell handelt es sich bei den gewünschten Eigenschaften um Abrieb, Rollwiderstand, gemessen durch die Rückprallelastizität, und Nassgriff. Dabei muss man berücksichtigen, dass eine Verbesserung in der einen Reifeneigenschaft oft eine Verschlechterung einer anderen Eigenschaft mit sich bringt. In einem gegebenen Mischungssystem existieren zum Beispiel verschiedene, bekannte Möglichkeiten die Abriebsfestigkeit heraufzusetzen. Zu erwähnen sind hier die Senkung der Glasübergangstemperatur der Kautschukmischung, die Optimierung des Füllgrades und der Wechsel des Polymersystems. Alle genannten Maßnahmen führen dabei zwangsläufig zu einer Verschlechterung der Nassgriffeigenschaften der gegebenen Mischung.Since the driving characteristics of a tire, in particular vehicle tires, depend to a large extent on the rubber composition of the tread, particularly high demands are placed on the composition of the tread compound. Thus, many attempts have been made to positively influence the properties of the tire by varying the polymer components, fillers and other additives in the tread compound. In principle, the desired properties are abrasion, rolling resistance, as measured by the rebound resilience, and wet grip. It should be remembered that an improvement in one tire property often results in a deterioration of another property. For example, in a given mixing system, there are several known ways to increase the abrasion resistance. Worth mentioning here are the reduction of the glass transition temperature of the rubber mixture, the optimization of the degree of filling and the change of the polymer system. All these measures inevitably lead to a deterioration of the wet grip properties of the given mixture.

Insbesondere die Beeinflussung der Glasübergangstemperatur durch Modifizierung der verwendeten Kautschuke und die Wahl geeigneter Polymerkomponenten wird in der Fachwelt vielfach diskutiert. Um Reifeneigenschaften wie Abrieb, Nassrutschverhalten und Rollwiderstand zu beeinflussen, ist es z. B. bekannt, Kautschuke mit unterschiedlichen Modifizierungen für die Kautschukmischungen zu verwenden.In particular, the influence on the glass transition temperature by modifying the rubbers used and the choice of suitable polymer components is widely discussed in the art. To influence tire properties such as abrasion, wet skid and rolling resistance, it is z. For example, it is known to use rubbers having various modifications for the rubber compounds.

Der diesbezügliche Stand der Technik soll nun näher vorgestellt werden.The relevant prior art will now be presented in more detail.

Die in dieser Schrift verwendete Angabe phr (parts per hundred parts of rubber by weight) ist dabei die in der Kautschukindustrie übliche Mengenangabe für Mischungsrezepturen. Die Dosierung der Gewichtsteile der einzelnen Substanzen wird dabei stets auf 100 Gewichtsteile der gesamten Masse aller in der Mischung vorhandenen Kautschuke bezogen.The term phr (parts per hundred parts of rubber by weight) used in this document is the quantity used in the rubber industry for mixture formulations. The dosage of the parts by weight of the individual substances is always based on 100 parts by weight of the total mass of all the rubbers present in the mixture.

Zum Stand der Technik sind folgende Druckschriften zu würdigen:

  • (D1) EP 0 102 045 B2
  • (D2) JP 2005220323 A
  • (D3) DE 698 23 479 T2
  • (D4) DE 698 02 245 T2
  • (D5) DE 601 19 370 T2
  • (D6) EP 0 794 224 A1
  • (D7) EP 1 270 657 A1
The following documents are to be appreciated from the prior art:
  • (D1) EP 0 102 045 B2
  • (D2) JP 2005220323 A
  • (D3) DE 698 23 479 T2
  • (D4) DE 698 02 245 T2
  • (D5) DE 601 19 370 T2
  • (D6) EP 0 794 224 A1
  • (D7) EP 1 270 657 A1

D1 offenbart eine Dienkautschukmischung, welche als Hauptkomponente ein lösungspolymerisiertes Styrolbutadiencopolymer mit einer Glastemperatur von nicht weniger als -50°C hat. Nicht weniger als 40 Gew. -% bis weniger als 65 Gew. -% der Polymerketten des lösungspolymerisierten Styrolbutadiencopolymers sind hierbei mit Siliziumtetrachlorid modifiziert und die Styrolbutadiencopolymere haben 40 Gew. -% oder weniger Vinylbindungen in dem Butadien. D1 discloses a diene rubber compound having as a main component a solution-polymerized styrene-butadiene copolymer having a glass transition temperature of not lower than -50 ° C. Not less than 40% by weight to less than 65% by weight of the polymer chains of the solution-polymerized styrene-butadiene copolymer are modified with silicon tetrachloride and the styrene-butadiene copolymers have 40% by weight or less of vinyl bonds in the butadiene.

Aus D2 ist eine Kautschukmischung bekannt, die eine Verbesserung hinsichtlich des Abriebs, der Griffigkeit auf der Fahrbahn und es Treibstoffverbrauchs zeigt. Die Kautschukmischung enthält hierbei ein konjugiertes Dienpolymer A und ein konjugiertes Dienpolymer B, dessen Glasübergangstemperatur 20 - 80°C niedriger als die des Polymers A ist und einen anorganischen Füllstoff. Bei Polymer B handelt es sich um ein modifiziertes Butadienpolymer oder ein Stryol-Butadien-Copolymer mit 10 - 40 Gew. -% Vinyl-Anteil.From D2 a rubber compound is known which shows an improvement in terms of abrasion, road grip and fuel consumption. The rubber composition here contains a conjugated diene polymer A and a conjugated diene polymer B whose glass transition temperature is 20-80 ° C lower than that of the polymer A and an inorganic filler. Polymer B is a modified butadiene polymer or a stryol-butadiene copolymer with 10 to 40 weight percent vinyl content.

Eine Kautschukmischung mit zwei verschiedenen Copolymeren wird in D3 offenbart. Das erste Copolymer ist modifiziert bzw. funktionalisiert, hat eine Glasumwandlungstemperatur zwischen 0 und -80°C und einen Vinyl-Anteil zwischen 5 und 50 Gew. -%, während das zweite Copolymer nicht modifiziert ist und eine Glasumwandlungstemperatur zwischen 0 und -80°C und einen Vinyl-Anteil zwischen 5 und 50 Gew. -% besitzt. Des Weiteren enthält die Kautschukmischung noch zwei Verstärkerfüllstoffe, u.a. zwischen 50 und 100 phr eines Füllstoffes aus Kieselerdebasis.A rubber blend with two different copolymers is disclosed in D3 . The first copolymer is modified or functionalized, has a glass transition temperature between 0 and -80 ° C and a vinyl content between 5 and 50 wt.%, While the second copolymer is unmodified and a glass transition temperature between 0 and -80 ° C and a vinyl content between 5 and 50 wt -.% Has. Furthermore, the rubber mixture contains two reinforcing fillers, among other things between 50 and 100 phr of a silica-based filler.

In D4 wird ein Luftreifen mit einer schwefel-vulkanisierbaren Zusammensetzung beschrieben, die gekennzeichnet ist durch 50 bis 90 phr eines Kautschuks mit einer Glasübergangstemperatur im Bereich von -80°C bis -110°C und 10 bis 50 phr mindestens eines Kautschuks mit einer Glasübergangstemperatur im Bereicht von -79°C bis +20°C und 15 bis 50 phr eines Harzes, das kein Kautschuk ist. Diese Mischung zeigt verbesserte Laboreigenschaften, welche mit einer verbesserten Reifenabnutzung bei gleichzeitiger Verbesserung der Griffigkeit und des Fahrverhaltens korrelieren. D4 discloses a pneumatic tire having a sulfur vulcanizable composition characterized by having from 50 to 90 phr of a rubber having a glass transition temperature in the range of -80 ° C to -110 ° C and 10 to 50 phr of at least one rubber having a glass transition temperature of Ranges from -79 ° C to + 20 ° C and 15 to 50 phr of a non-rubber resin. This blend shows improved lab performance, which correlates with improved tire wear while improving grip and handling.

D5 beschreibt eine elastomere, schwefelvulkanisierbare Zusammensetzung für die Herstellung von Reifen zur Reduzierung der Hysterese und somit zur Verringerung des Treibstoffverbrauchs. Diese Mischung umfasst einen Blend aus 20 bis 100 Gew.-% eines funktionalisierten Elastomers mit 10 bis 150 phr Siliziumdioxid und mit 0 phr Ruß und 0 bis 80 Gew.-% eines nicht-funktionalisierten Elastomers. D5 describes an elastomeric, sulfur vulcanizable composition for the manufacture of tires for reducing hysteresis and thus reducing fuel consumption. This blend comprises a blend of from 20 to 100 weight percent of a functionalized elastomer having 10 to 150 phr of silica and having 0 phr of carbon black and 0 to 80 weight percent of a non-functionalized elastomer.

D6 beschreibt Kautschukzusammensetzungen für Reifen die einen mit N-Methyl-ε-caprolactam modifizierten Styrolbutadienkautschuk und einen hochmolekularen Styrolbutadienkautschuk enthalten. D6 describes rubber compositions for tires containing a styrene-butadiene rubber modified with N-methyl-ε-caprolactam and a high molecular weight styrene-butadiene rubber.

D7 beschreibt eine Kautschukmischung für Laufstreifen von Reifen die einen endgruppenmodifizierten Styrolbutadien Kautschuk, mindestens einen weiteren Kautschuk und eine relativ große Menge an Kieselsäure enthält. D7 describes a rubber composition for treads of tires containing an end-group modified styrene butadiene rubber, at least one other rubber and a relatively large amount of silica.

Der vorliegenden Erfindung liegt nun die Aufgabe zu Grunde, Kautschukmischungen bereitzustellen, deren Vulkanisate sich durch einen erhöhten Nassgriff auszeichnen, wobei gleichzeitig der Rollwiderstand auf gleichem Niveau verbleibt oder sogar verbessert wird.The present invention is based on the object to provide rubber mixtures whose vulcanizates are characterized by an increased wet grip, at the same time the rolling resistance remains at the same level or even improved.

Gelöst wird die Aufgabe dadurch, dass die Kautschukmischung der eingangs genannten Art zumindest durch folgende Zusammensetzung gekennzeichnet ist:

  • 20 - 90 phr zumindest eines natürlichen oder synthetischen Polyisoprens und
  • 5 - 40 phr zumindest eines Butadienkautschuks und
  • 5 - 50 phr zumindest eines endgruppenmodifizierten Styrolbutadienkautschuks und
  • 0 - 50 phr zumindest eines weiteren polaren oder unpolaren Kautschuks und
  • 0 - 7 phr zumindest eines Weichmacheröls und
  • 0,1 - 20 phr amorphe Kieselsäure und / oder Fällungskieselsäure und
  • 30 - 70 phr zumindest eines Rußes und
  • 2 - 100 phr weitere Zusatzstoffe,
wobei der Styrolbutadienkautschuk eine Glasübergangstemperatur zwischen -40°C und 0°C hat und mit Aminogruppen und/oder Alkoxysilylgruppen und/oder OH-Gruppen und/oder Epoxidgruppen und/oder Carboxylgruppen und/oder Mercaptogruppen endgruppenmodifiziert ist.The object is achieved in that the rubber mixture of the type mentioned above is characterized at least by the following composition:
  • 20 - 90 phr of at least one natural or synthetic polyisoprene and
  • 5 - 40 phr of at least one butadiene rubber and
  • 5 - 50 phr of at least one end-group modified styrene-butadiene rubber and
  • 0 - 50 phr of at least one other polar or nonpolar rubber and
  • 0 - 7 phr of at least one processing oil and
  • 0.1-20 phr of amorphous silica and / or precipitated silica and
  • 30 - 70 phr of at least one soot and
  • 2 - 100 phr further additives,
wherein the styrene-butadiene rubber has a glass transition temperature between -40 ° C and 0 ° C and end-modified with amino groups and / or alkoxysilyl groups and / or OH groups and / or epoxy groups and / or carboxyl groups and / or mercapto groups.

Überraschenderweise wurde gefunden, dass durch obig beschriebene Kautschukmischung der Nassgriff sich verbessert und der Rollwiderstand auf dem gleichen Niveau verbleibt oder sich sogar verbessert. Dadurch ist es möglich den entsprechenden Zielkonflikt zwischen Nassgriff und Rollwiderstand zu entkoppeln. Dies gilt nicht nur für den Fahrzeuglaufstreifen, sondern auch für weitere innere Reifenbauteile. Die Kautschukmischungen für die weiteren inneren Reifenbauteile werden im Folgenden zusammengefasst, und wie in der Reifentechnologie üblich, auch als body compounds oder body-Mischungen bezeichnet.Surprisingly, it has been found that the wet grip improved by the rubber mixture described above and the rolling resistance remains at the same level or even improved. This makes it possible to decouple the corresponding target conflict between wet grip and rolling resistance. This applies not only to the vehicle tread, but also to other inner tire components. The rubber compounds for the other inner tire components are summarized below, and as commonly used in tire technology, also referred to as body compounds or body mixtures.

Weitere Anwendung findet die erfindungsgemäße Kautschukmischung in der Mischungsentwicklung für Riemen und Gurte, insbesondere für Fördergurte.Further application of the rubber mixture according to the invention in the development of mixtures for belts and straps, especially for conveyor belts.

Im täglichen Einsatz, vor allem bei Betrieb im Außenbereich, unterliegt insbesondere die Laufseite von Fördergurten starken mechanischen Beanspruchungen, z. B. bei Umlenkung an Antriebs-, Umlenk- und / oder Knicktrommeln und Aushalten der auftretenden Zugkräfte. Daher sind die Griffigkeit auch bei nassen oder feuchten Witterungsverhältnissen sowie die Rückprallelastizität, bei gleich bleibenden weiteren viskoelastischen Eigenschaften, zur Sicherung einer langen Lebensdauer und zur Arbeitssicherheit von großer Bedeutung.In daily use, especially in outdoor operation, in particular the running side of conveyor belts subject to strong mechanical stresses, eg. As in deflection of drive, deflection and / or buckling drums and endurance of the tensile forces occurring. Therefore, the grip even in wet or damp weather conditions and the resilience, while maintaining other viscoelastic properties, to ensure a long life and safety at work are of great importance.

Die Kautschukmischung enthält 20 - 90 phr, bevorzugt 25 - 80 phr, besonders bevorzugt 45 - 80 phr zumindest eines natürlichen oder synthetischen Polyisoprens.The rubber mixture contains 20-90 phr, preferably 25-80 phr, more preferably 45-80 phr of at least one natural or synthetic polyisoprene.

Des Weiteren sind in der Kautschukmischung 5 - 40 phr, bevorzugt 5 - 30 phr zumindest eines Butadienkautschuks enthalten. In einer besonderen Ausführungsform ist der Butadienkautschuk ein high-cis Butadienkautschuk mit einem cis-Anteil größer oder gleich 90 Gew. -%.Furthermore, 5 to 40 phr, preferably 5 to 30 phr of at least one butadiene rubber are contained in the rubber mixture. In a particular embodiment, the butadiene rubber is a high-cis butadiene rubber with a cis content greater than or equal to 90% by weight.

Zumindest ein endgruppenmodifizierter Styrolbutadienkautschuk ist in Mengenanteilen von 5 - 50 phr, bevorzugt in Mengenanteilen von 10 - 40 phr in der Kautschukmischung vorhanden. Es handelt sich hierbei bevorzugt um einen lösungspolymerisierten Styrolbutadienkautschuk oder um einen emulsionspolymerisierten Styrolbutadienkautschuk. Der Styrolbutadienkautschuk hat eine Glasübergangstemperatur zwischen -40°C und 0°C, bevorzugt zwischen -35°C und 0°C und besonders bevorzugt zwischen -30°C und -10°C.At least one end-group-modified styrene-butadiene rubber is present in proportions of from 5 to 50 phr, preferably in proportions of from 10 to 40 phr, in the rubber mixture. It is preferably a solution-polymerized styrene-butadiene rubber or an emulsion-polymerized styrene-butadiene rubber. The styrene-butadiene rubber has a glass transition temperature between -40 ° C and 0 ° C, preferably between -35 ° C and 0 ° C, and more preferably between -30 ° C and -10 ° C.

Der Styrolgehalt des Styrolbutadienkautschuks ist bevorzugt kleiner oder gleich 50 Gew. - % und / oder der Vinylgehalt des Styrolbutadienkautschuks ist bevorzugt größer oder gleich 10 Gew. -%.The styrene content of the styrene-butadiene rubber is preferably less than or equal to 50% by weight and / or the vinyl content of the styrene-butadiene rubber is preferably greater than or equal to 10% by weight.

Der Styrolbutadienkautschuk ist mit Aminogruppen und / oder Alkoxysilylgruppen und / oder OH-Gruppen und / oder Epoxidgruppen und / oder Carboxylgruppen und / oder Mercaptogruppen endgruppenmodifiziert.The styrene-butadiene rubber is end-group-modified with amino groups and / or alkoxysilyl groups and / or OH groups and / or epoxide groups and / or carboxyl groups and / or mercapto groups.

In der Kautschukmischung sind 0 - 50 phr, bevorzugt wenigstens 0,1 phr, insbesondere wenigstens 0,5 phr, zumindest eines weiteren polaren und / oder unpolaren Kautschuks enthalten. Der weitere polare und / oder unpolare Kautschuk ist hierbei ausgewählt aus der Gruppe bestehend aus Flüssigkautschuken und / oder Halobutylkautschuk und / oder Polynorbornen und / oder Isopren-Isobutylen-Copolymer und / oder Ethylen-Propylen-Dien-Kautschuk und / oder Nitrilkautschuk und / oder Chloroprenkautschuk und / oder Acrylat-Kautschuk und / oder Fluorkautschuk und / oder Silikon-Kautschuk und / oder Polysulfidkautschuk und / oder Epichlorhydrinkautschuk und / oder Styrol-Isopren-Butadien-Terpolymer. Zusätzlich kann die Kautschukmischung auch noch weitere Dienkautschuke enthalten, die nicht den kennzeichnenden Merkmalen der Ansprüche 1 bis 13 entsprechen.The rubber mixture contains 0-50 phr, preferably at least 0.1 phr, in particular at least 0.5 phr, of at least one further polar and / or nonpolar rubber. The further polar and / or non-polar rubber is in this case selected from the group consisting of liquid rubbers and / or halobutyl rubber and / or polynorbornene and / or isoprene-isobutylene copolymer and / or ethylene-propylene-diene rubber and / or nitrile rubber and / or Chloroprene rubber and / or acrylate rubber and / or fluororubber and / or silicone rubber and / or polysulfide rubber and / or epichlorohydrin rubber and / or styrene-isoprene-butadiene terpolymer. In addition, the rubber mixture may also contain other diene rubbers which do not correspond to the characterizing features of claims 1 to 13.

Die erfindungsgemäße Kautschukmischung enthält weiterhin 0 - 7 phr, bevorzugt wenigstens aber 0,1 phr, insbesondere wenigstens 0,5 phr, zumindest eines Weichmacheröls, wobei das Weichmacheröl bevorzugt ein Mineralöl ist, das ausgewählt ist aus der Gruppe, bestehend aus DAE (Destillated Aromatic Extracts) und / oder RAE (Residual Aromatic Extract) und / oder TDAE (Treated Destillated Aromatic Extracts) und / oder MES (Mild Extracted Solvents) und / oder naphtenische Öle.The rubber mixture according to the invention also contains 0-7 phr, preferably at least 0.1 phr, in particular at least 0.5 phr, of at least one plasticizer oil, wherein the plasticizer oil is preferably a mineral oil which is selected from the group consisting of DAE (Distilled Aromatic Extracts) and / or RAE (Residual Aromatic Extract) and / or TDAE (Treated Distilled Aromatic Extracts) and / or MES (Mild Extracted Solvents) and / or naphthenic oils.

Es können in der Kautschukmischung noch 0 - 5 phr zumindest eines weiteren zusätzlichen Weichmachers vorhanden sein. Dieser weitere Weichmacher kann ein synthetischer Weichmacher und / oder eine Fettsäure und / oder ein Fettsäurederivat und / oder ein Harz und / oder ein Faktis sein.There may be in the rubber mixture still 0 - 5 phr of at least one additional additional plasticizer. This further plasticizer may be a synthetic plasticizer and / or a fatty acid and / or a fatty acid derivative and / or a resin and / or a factor.

Die Kautschukmischung enthält 0,1 - 20 phr, bevorzugt wenigstens 0,5 phr, amorphe Kieselsäure und / oder Fällungskieselsäure. Es können dabei alle dem Fachmann für die Reifenindustrie bekannten Kieselsäuren eingesetzt werden. Die amorphe Kieselsäure und / oder Fällungskieselsäure ist durch ein Kupplungsagenz, bevorzugt zumindest ein Silan, and die Polymermatrix angebunden.The rubber mixture contains 0.1-20 phr, preferably at least 0.5 phr, of amorphous silica and / or precipitated silica. All the silicas known to the person skilled in the tire industry can be used. The amorphous silica and / or precipitated silica is attached to the polymer matrix by a coupling agent, preferably at least one silane.

Das Silan wird in Mengenanteilen von 0 - 10 phr, bevorzugt in Mengenanteilen von 0 - 8 phr, besonders bevorzugt wenigstens aber 0,1 phr, insbesondere wenigstens 0,5 phr, eingesetzt. Die Silan-Kupplungsagenzien dienen gleichzeitig zur Verbesserung der Verarbeitbarkeit und zur Anbindung der Kieselsäure und anderer ggf. vorhandener polarer Füllstoffe an den Dienkautschuk und reagieren mit den oberflächlichen Silanolgruppen der Kieselsäure oder anderen polaren Gruppen während des Mischens des Kautschuks bzw. der Kautschukmischung (in situ) oder bereits vor der Zugabe des Füllstoffes zum Kautschuk im Sinne einer Vorbehandlung (Vormodifizierung). Als Silan-Kupplungsagenzien können dabei alle dem Fachmann für die Verwendung in Kautschukmischungen bekannten Silan-Kupplungsagenzien verwendet werden.The silane is used in proportions of 0-10 phr, preferably in proportions of 0-8 phr, more preferably at least 0.1 phr, especially at least 0.5 phr. The silane coupling agents serve at the same time to improve the processability and to attach the silica and other optional polar fillers to the diene rubber and react with the silanol superficial groups of the silica or other polar groups during the mixing of the rubber or rubber compound (in situ). or even before the addition of the filler to the rubber in the sense of a pretreatment (pre-modification). All silane coupling agents known to the person skilled in the art for use in rubber mixtures can be used as silane coupling agents.

Des Weiteren enthält die Kautschukmischung 30 - 70 phr zumindest eines Rußes, bevorzugt mit einer DPB-Zahl zwischen 105 und 150 cm3 / 100g. Die DBP-Zahl gemäß ASTM D 2414 bestimmt das spezifische Absorptionsvolumen eines Rußes oder eines hellen Füllstoffes mittels Dibutyl-phthalat.Further includes the rubber mixture contains 30 - 70 phr of at least one carbon black, preferably having a DPB number 105-150 cm 3 / 100g. The DBP number according to ASTM D 2414 determines the specific absorption volume of a carbon black or a light filler by means of dibutyl phthalate.

Die Kautschukmischung kann neben Kieselsäure und / oder Ruß auch noch weitere Füllstoffe wie Aluminiumhydroxid, Schichtsilikate, Kreide, Stärke, Magnesiumoxid, Titandioxid, Kautschukgele, Kurzfasern usw. in beliebigen Kombinationen enthalten.In addition to silica and / or carbon black, the rubber mixture may also contain further fillers such as aluminum hydroxide, layered silicates, chalk, starch, magnesium oxide, titanium dioxide, rubber gels, short fibers, etc. in any desired combinations.

Des Weiteren enthält die Kautschukmischung noch weitere Zusatzstoffe.
Weitere Zusatzstoffe beinhaltet im Wesentlichen das Vernetzungssystem (Vernetzer, Beschleuniger und Verzögerer), Ozonschutzmittel, Alterungsschutzmittel, Mastikationshilfsmittel und Aktivatoren.
Der Mengenanteil der Gesamtmenge an weiteren Zusatzstoffen beträgt 2 bis 100 phr, bevorzugt 3 bis 80 phr und besonders bevorzugt 5 - 60 phr.Furthermore, the rubber mixture contains other additives.
Other additives essentially include the crosslinking system (crosslinker, accelerator and retarder), antiozonants, anti-aging agents, masticating agents and activators.
The proportion of the total amount of further additives is from 2 to 100 phr, preferably from 3 to 80 phr and more preferably from 5 to 60 phr.

Die Vulkanisation der Kautschukmischung wird in Anwesenheit von Schwefel oder Schwefelspendern durchgeführt, wobei einige Schwefelspender zugleich als Vulkanisationsbeschleuniger wirken können. Schwefel oder Schwefelspender werden im letzten Mischungsschritt in den vom Fachmann gebräuchlichen Mengen (0,4 bis 4 phr, Schwefel, bevorzugt in Mengen von 1,0 bis 2,5 phr) der Kautschukmischung zugesetzt. Zur Kontrolle der erforderlichen Zeit und / oder Temperatur der Vulkanisation und zur Verbesserung der Vulkanisateigenschaften kann die Kautschukmischung vulkanisationsbeeinflussende Substanzen wie Vulkanisationsbeschleuniger, Vulkanisationsverzögerer und Vulkanisationsaktivatoren in den üblichen Mengen enthalten, die erfindungsgemäß in den obig beschriebenen Zusatzstoffen enthaltend sind.The vulcanization of the rubber mixture is carried out in the presence of sulfur or sulfur donors, with some sulfur donors can also act as a vulcanization accelerator. Sulfur or sulfur donors are added to the rubber mixture in the last mixing step in amounts customary to the person skilled in the art (0.4 to 4 phr, sulfur, preferably in amounts of 1.0 to 2.5 phr). To control the required time and / or temperature of the vulcanization and to improve the vulcanizate properties, the rubber mixture may contain vulcanization-influencing substances such as vulcanization accelerators, vulcanization retarders and vulcanization activators in the usual amounts, which are contained according to the invention in the above-described additives.

Die Herstellung der erfindungsgemäßen Kautschukmischung erfolgt nach dem in der Kautschukindustrie üblichen Verfahren, bei dem zunächst in ein oder mehreren Mischstufen eine Grundmischung mit allen Bestandteilen außer dem Vulkanisationssystem (Schwefel und vulkanisationsbeeinflussende Substanzen) hergestellt wird. Durch Zugabe des Vulkanisationssystems in einer letzten Mischstufe wird die Fertigmischung erzeugt. Die Fertigmischung wird z.B. durch einen Extrusionsvorgang weiterverarbeitet und in die entsprechende Form gebracht.The preparation of the rubber mixture according to the invention is carried out according to the usual method in the rubber industry, in which first in one or more mixing stages, a base mixture with all components except the vulcanization system (sulfur and vulcanisationsbeeinflussende substances) is prepared. By adding the vulcanization system in a final mixing stage, the finished mixture is produced. The finished mixture is further processed eg by an extrusion process and brought into the appropriate form.

Die Kautschukmischung wird zur Herstellung von Fahrzeugluftreifen, insbesondere eines Laufstreifens und / oder einer Body-Mischung verwendet. Als Body-Mischungen werden hier die Mischungen bezeichnet, aus denen die inneren Bauteile eines Fahrzeugreifens bestehen.The rubber mixture is used for the production of pneumatic vehicle tires, in particular a tread and / or a body mixture. As body mixtures are here called the mixtures that make up the inner components of a vehicle tire.

Zur Verwendung in Fahrzeugluftreifen wird die Mischung bevorzugt in die Form eines Laufstreifens gebracht und bei der Herstellung des Fahrzeugreifenrohlings wie bekannt aufgebracht. Der Laufstreifen kann aber auch in Form eines schmalen Kautschukmischungsstreifens auf einen Reifenrohling aufgewickelt werden. Die Herstellung der erfindungsgemäßen Kautschukmischung zur Verwendung als Body-Mischung in Fahrzeugreifen erfolgt wie bereits für den Laufstreifen beschrieben. Der Unterschied liegt in der Formgebung nach dem Extrusionsvorgang. Die so erhaltenen Formen der erfindungsgemäßen Kautschukmischung für eine oder mehrere unterschiedliche Body-Mischungen dienen dann dem Aufbau eines Reifenrohlings.For use in pneumatic vehicle tires, the mixture is preferably made in the form of a tread and applied as known in the manufacture of the vehicle tire blank. The tread may also be wound up in the form of a narrow rubber mix strip on a green tire. The preparation of the rubber mixture according to the invention for use as a body mixture in vehicle tires is carried out as already described for the tread. The difference lies in the shape after the extrusion process. The thus obtained forms of the rubber mixture according to the invention for one or more different body mixtures then serve the construction of a green tire.

Die Kautschukmischung wird zur Herstellung von Riemen und Gurten, insbesondere Fördergurten, Flachriemen, Keilriemen, Keilrippenriemen und Zahnriemen verwendet. Zur Verwendung der erfindungsgemäßen Kautschukmischung in Riemen und Gurten wird die extrudierte Mischung in die entsprechende Form gebracht und dabei oder nachher häufig mit Festigkeitsträgern, z.B. synthetische Fasern oder Stahlcorde, versehen. Zumeist ergibt sich so ein mehrlagiger Aufbau, bestehend aus einer und / oder mehrerer Lagen Kautschukmischung, einer und / oder mehrerer Lagen gleicher und / oder verschiedener Festigkeitsträger und einer und / oder mehreren weiteren Lagen dergleichen und / oder einer anderen Kautschukmischung.The rubber compound is used for the production of belts and straps, in particular conveyor belts, flat belts, V-belts, V-ribbed belts and toothed belts. To use the rubber composition of the present invention in belts and straps, the extruded mixture is formed into the appropriate shape and often or subsequently reinforced with reinforcing materials, e.g. synthetic fibers or steel cords. In most cases, this results in a multi-layered structure, consisting of one and / or several layers of rubber mixture, one and / or more layers of identical and / or different reinforcement and one and / or several other layers of the like and / or another rubber mixture.

Die Erfindung soll nun anhand von Vergleichs- und Ausführungsbeispielen, die in Tabellen 1a und 1b zusammengefasst sind, näher erläutert werden.The invention will now be explained in more detail by means of comparison and exemplary embodiments, which are summarized in Tables 1a and 1b.

Bei sämtlichen in der Tabelle enthaltenen Mischungsbeispielen sind die angegebenen Mengenangaben Gewichtsteile, die auf 100 Gewichtsteile Gesamtkautschuk bezogen sind (phr).For all mixing examples contained in the table, the quantities given are parts by weight based on 100 parts by weight of total rubber (phr).

Die Mischungsherstellung erfolgte unter üblichen Bedingungen in zwei Stufen in einem Labortangentialmischer. Aus sämtlichen Mischungen wurden Prüfkörper durch Vulkanisation hergestellt und mit diesen Prüfkörpern für die Kautschukindustrie typische Materialeigenschaften bestimmt. Für die obig beschriebenen Tests an Prüfkörpern wurden folgende Testverfahren angewandt:

  • Shore-A-Härte bei Raumtemperatur (RT) gemäß DIN 53 505
  • Rückprallelastizität bei Raumtemperatur (RT) und 70°C gemäß DIN 53 512
  • Spannungswerte bei 300 % Dehnung bei Raumtemperatur gemäß DIN 53 504
Mixture preparation was carried out under standard conditions in two stages in a laboratory tangential mixer. From all mixtures test specimens were prepared by vulcanization and determined with these specimens typical for the rubber industry material properties. For the above-described tests on specimens, the following test procedures were used:
  • Shore A hardness at room temperature (RT) according to DIN 53 505
  • Rebound resilience at room temperature (RT) and 70 ° C according to DIN 53 512
  • Tension values at 300% elongation at room temperature in accordance with DIN 53 504

Bei sämtlichen in der Tabelle enthaltenen Mischungsbeispielen sind die angegebenen Mengenangaben, wie bereits beschrieben, Gewichtsteile, die auf 100 Gewichtsteile Gesamtkautschuk bezogen sind (phr). Die Vergleichsmischungen sind mit V1 bis V4 für verschiedene Referenzmischungen ohne das erfindungsgemäße Polymersystem bzw. E für eine Mischung mit Verwendung des erfindungsgemäßen Polymersystems gekennzeichnet. Tabelle 1a zeigt die jeweiligen Mischungszusammensetzungen und Tabelle 1b die entsprechenden Prüfergebnisse. Tabelle 1a Bestandteile Einheit V1 V2 V3 V4 E Polyisopren phr 100 85 50 50 50 BRa phr -- 15 15 15 15 SSBRb phr -- -- 35 35 35 Styrolanteil des SSBR Gew. -% -- -- 15 25 21 Vinylanteil des SSBR Gew. -% -- -- 29 30 61 Glasübergangstemperatur des SSBR °C -- -- -55 -53 -27 Endgruppenfunktionalisierung des SSBRc -- -- -- Ja Nein Ja Ruß N-121 phr 46 46 46 46 46 Silika phr 5 5 5 5 5 Weichmacheröld phr 1 1 1 1 1 Vulkanisationssysteme phr 2,7 2,7 2,7 2,7 2,7 a High-cis Polybutadien , cis-Anteil ≥ 95 Gew. -%
b SSBR Styrolbutadienkautschuk
c durch Aminosilanfunktionalisierung endgruppenmodifiziert
d Mineralöl, TDAE
e Vulkanisationssystem enthält: Schwefel, Beschleuniger (CBS), Verzögerer (CTP) Tabelle 1b Eigenschaften Einheit V1 V2 V3 V4 E Härte bei RT Shore A 63,0 63,5 62,9 64,3 63,2 Rückprall RT % 48,7 50,3 51,7 42,1 44,2 Rückprall 70°C % 62,1 61,8 61,3 52,7 60,1 Spannungswert 300% MPa 13,8 13,4 13,1 12,7 14 For all mixture examples contained in the table, the quantities given are, as already described, parts by weight based on 100 parts by weight of total rubber (phr). The comparison mixtures are labeled with V1 to V4 for various reference mixtures without the polymer system according to the invention or E for a mixture with use of the polymer system according to the invention. Table 1a shows the respective blend compositions and Table 1b the corresponding test results. <b> Table 1a </ b> ingredients unit V1 V2 V3 V4 e polyisoprene phr 100 85 50 50 50 BR a phr - 15 15 15 15 SSBR b phr - - 35 35 35 Styrene content of the SSBR Weight% - - 15 25 21 Vinyl portion of the SSBR Weight% - - 29 30 61 Glass transition temperature of the SSBR ° C - - -55 -53 -27 End-group functionalization of the SSBR c - - - Yes No Yes Soot N-121 phr 46 46 46 46 46 silica phr 5 5 5 5 5 Processing oil d phr 1 1 1 1 1 Vulcanization system e phr 2.7 2.7 2.7 2.7 2.7 a high-cis polybutadiene, cis content ≥ 95% by weight
b SSBR styrene butadiene rubber
c end-modified by aminosilane functionalization
d mineral oil, TDAE
e vulcanization system contains: sulfur, accelerator (CBS), retarder (CTP) properties unit V1 V2 V3 V4 e Hardness at RT Shore A 63.0 63.5 62.9 64.3 63.2 Rebound RT % 48.7 50.3 51.7 42.1 44.2 Rebound 70 ° C % 62.1 61.8 61.3 52.7 60.1 Voltage value 300% MPa 13.8 13.4 13.1 12.7 14

Der Nassgriff der Kautschukmischung wird im Labormaßstab durch die Rückprallelastizität bei Raumtemperatur und der Rollwiderstand durch die Rückprallelastizität bei 70°C ausgedrückt. Diese beiden Indikatoren bilden den Zielkonflikt, der durch die erfindungsgemäße Kautschukmischung E gelöst oder zumindest entschärft werden soll.The wet grip of the rubber composition is expressed on a laboratory scale by the rebound resilience at room temperature and the rolling resistance by the rebound resilience at 70 ° C. These two indicators form the conflict of objectives which is to be solved or at least defused by the rubber mixture E according to the invention.

Mischung V1 enthält als Polymerkomponente nur Polyisopren. Durch den anteiligen Austausch von Polyisopren durch Butadienkautschuk, wie durch V2 dargestellt, verschlechtert sich der Nassgriff, dadurch dass der Wert für die Rückprallelastizität bei RT vergleichsweise größer wird, ohne dass sich der Rollwiderstand verschlechtert. Wird weiterhin anteilig Polyisopren durch einen endgruppenmodifizierten Styrolbutadienkautschuk mit einer niedrigen Glasübergangstemperatur, siehe V3, ausgetauscht, so zeigt sich keine Verbesserung des Nassgriffs. Bei anteiligem Austausch durch einen nicht endgruppenmodifizierten Styrolbutadienkautschuk mit einer niedrigen Glasübergangstemperatur, siehe V4, bringt zwar die gewünschte Verbesserung des Nassgriffs, gleichzeitig aber eine nicht akzeptable Verschlechterung des Rollwiderstandes, dadurch das der Wert für die Rückprallelastizität niedriger wird, mit sich.Mixture V1 contains only polyisoprene as the polymer component. The replacement of polyisoprene by butadiene rubber, as represented by V2, worsens the wet grip, making the value of the rebound resilience at RT relatively high without deteriorating the rolling resistance. If a proportionate amount of polyisoprene is exchanged for an end-group-modified styrene-butadiene rubber with a low glass transition temperature, see V3, there is no improvement in the wet grip. Replacing it with a non-endgroup modified styrene butadiene rubber having a low glass transition temperature, see V4, brings with it the desired wet grip improvement, but at the same time unacceptable degradation of the rolling resistance, thereby lowering the value of the rebound resilience.

Erst durch die erfindungsgemäße Kautschukmischung, siehe E, wird dieser Zielkonflikt entschärft. In diesem Ausführungsbeispiel wird ein endgruppenmodifizierter Styrolbutadienkautschuk mit einer vergleichsweise hohen Glasübergangstemperatur eingesetzt.Only through the rubber mixture according to the invention, see E, is this target conflict defused. In this embodiment, an end group-modified styrene-butadiene rubber having a comparatively high glass transition temperature is used.

Claims (11)

  1. Rubber mixture characterized by the following composition:
    - from 20 - 90 phr of at least one natural or synthetic polyisoprene and
    - from 5 - 40 phr of at least one butadiene rubber and
    - from 5 - 50 phr of at least one end-group-modified styrene-butadiene rubber and
    - from 0 - 50 phr of at least one other polar or nonpolar rubber and
    - from 0 - 7 phr of at least one plasticizer oil and
    - from 0.1 - 20 phr of amorphous silica and/or precipitated silica and
    - from 30 to 70 phr of at least one carbon black and
    - from 2 to 100 phr of other additives,
    where the glass transition temperature of the styrene-butadiene rubber is from -40°C to 0°C and the styrene-butadiene rubber has end-group modification by amino groups and/or by alkoxysilyl groups and/or by OH groups and/or by epoxy groups and/or by carboxy groups and/or by mercapto groups.
  2. Rubber mixture according to Claim 1, characterized in that it comprises from 25 - 80 phr of a natural or synthetic polyisoprene.
  3. Rubber mixture according to Claim 1 or 2, characterized in that it comprises from 5 - 30 phr of a butadiene rubber.
  4. Rubber mixture according to Claim 1 or 3, characterized in that it comprises from 10-40 phr of a styrene-butadiene rubber.
  5. Rubber mixture according to Claim 1 or 4, characterized in that the styrene content of the styrene-butadiene rubber is less than or equal to 50% by weight and/or the vinyl content of the styrene-butadiene rubber is greater than or equal to 10% by weight.
  6. Rubber mixture according to any of Claims 1 to 5, characterized in that the DBP number of the carbon black is from 105 to 150 cm3/100 g.
  7. Use of a rubber mixture according to any of Claims 1 to 6 for the production of a tyre.
  8. Use of a rubber mixture according to Claim 7 for the production of the tread of a tyre.
  9. Use of a rubber mixture according to Claim 7 for the production of a body mixture of a tyre.
  10. Use of a rubber mixture according to Claim 9 for the production of a body mixture of a tyre, comprising side wall, inner lining, apex, belt, shoulder, belt profile, squeegee, carcass, bead reinforcement, and/or bandage.
  11. Use of a rubber mixture according to any of Claims 1 to 6 for the production of a drive belt or other belt.
EP08861687.5A 2007-12-18 2008-10-31 Rubber mixture, particularly for vehicle tires Active EP2225323B1 (en)

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EP08861687.5A Active EP2225323B1 (en) 2007-12-18 2008-10-31 Rubber mixture, particularly for vehicle tires

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EP (1) EP2225323B1 (en)
BR (1) BRPI0821360B1 (en)
DE (1) DE102007060859A1 (en)
WO (1) WO2009077256A1 (en)

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US11214667B2 (en) 2019-07-29 2022-01-04 The Goodyear Tire & Rubber Company Pneumatic tire
US11441018B2 (en) 2019-09-12 2022-09-13 The Goodyear Tire & Rubber Company Pneumatic tire having tread with three elastomers
US11441021B2 (en) 2019-07-29 2022-09-13 The Goodyear Tire & Rubber Company Pneumatic tire

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DE102009044190A1 (en) * 2009-10-07 2011-05-05 Continental Reifen Deutschland Gmbh Sulfur crosslinkable rubber compound and tires
ES2612554T3 (en) * 2013-09-27 2017-05-17 Continental Reifen Deutschland Gmbh Crosslinkable rubber mixture with sulfur
DE102016213625A1 (en) * 2016-07-26 2018-02-01 Contitech Vibration Control Gmbh Rubber mixture and elastic article containing the rubber mixture
EP3728453B1 (en) * 2017-12-19 2021-12-01 Compagnie Generale Des Etablissements Michelin Tread of a tire containing a crosslinking system bases on organic peroxide
US20240043587A1 (en) * 2022-07-28 2024-02-08 The Goodyear Tire & Rubber Company Rubber composition and truck tire

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US5901766A (en) 1997-08-26 1999-05-11 The Goodyear Tire & Rubber Company Pneumatic tire having a tread compound containing high levels of low Tg polymer and resin
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11214667B2 (en) 2019-07-29 2022-01-04 The Goodyear Tire & Rubber Company Pneumatic tire
US11441021B2 (en) 2019-07-29 2022-09-13 The Goodyear Tire & Rubber Company Pneumatic tire
US11441018B2 (en) 2019-09-12 2022-09-13 The Goodyear Tire & Rubber Company Pneumatic tire having tread with three elastomers

Also Published As

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DE102007060859A1 (en) 2009-06-25
EP2225323A1 (en) 2010-09-08
WO2009077256A1 (en) 2009-06-25
BRPI0821360B1 (en) 2018-10-30
BRPI0821360A2 (en) 2015-06-16

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